Solar Energy 244 (2022) 75–83

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Futuristic kusachiite solar cells of CuBi2O4 absorber and metal sulfide

buffer Layers: Theoretical efficiency approaching 28 %
Yashwanth K. Reddy 1, Vishesh Manjunath 1, Santosh Bimli, Rupesh S. Devan *
Department of Metallurgy Engineering and Materials Science, Indian Institute of Technology Indore, Simrol, Khandwa Road, Madhya Pradesh 453552, India

A R T I C L E I N F O A B S T R A C T

Keywords: Solar cells exhibit high performance using a thin semiconducting film with superior light-harvesting ability.
CuBi2O4 light absorber Though a variety of thin-film solar cells have shown promise, the quest to find cheaper and promising alter­
Kusachiite solar cells natives is necessary. Herein, this study provides evidence of the capabilities of cheap and stable copper bismuth
SCAPS-1D
oxide or CuBi2O4 (CBO) as an efficient light absorber for thin-film photovoltaics. Solar Cell Capacitance
Metal sulfide buffer layer
Doping
Simulator-1D (SCAPS-1D) software is used to optimize the performance of CBO-based kusachiite solar cells with
Defect density various n-type metal sulfide (MS) buffer layers (CdS, WS2, SnS2, and ZnS). The variation in the thickness and
acceptor and donor doping density of CBO light absorber and MSs buffer layers film had the highest control over
power conversion efficiency (PCE) and other solar cell parameters. The effect of the work function of metal back
contact and operating temperature on the performance of solar cells is also analyzed to assess the real-time
application of the proposed metal sulfide and CBO-based kusachiite solar cells. The solar cell device structure
of ITO/WS2/CBO/Au optimized in terms of thickness and doping density has shown a theoretical PCE of 22.84 %.

1. Introduction photovoltaic properties, the synthesis of thin-film absorbers in required

The efficient utilization of solar energy to produce electricity has
been the subject of intensive research because of the rapid increase in
global energy demands and the need to reduce the emission of green­
house gases from electricity generation by fossil fuels (Al-Shahri et al.,
2021). Solar energy conversion to electricity is an utterly clean energy
source that can fulfill global energy demands with minimal detrimental
impact on the environment (Green, 2019). Therefore, tremendous ef­
forts have been made to develop cost-effective high PCE solar cells.
Though the implementation of environmentally benign first-generation
crystalline Si solar cells, with excellent charge transport properties and
stability, is worthwhile with recently reduced cost, long pay pack time
with modest PCE is demanding to look for a better alternative. The
second-generation thin-film solar cells, i.e., CIGS, CZTS, CdTe, etc., (He,
M. et al., 2021) fabricated over flexible or rigid transparent substrates
are found to be prolific alternatives to deliver promising efficiencies.
Their ease of packaging, high power to weight ratio, flexibility, and roll
to roll processing (Kurley et al., 2021; Wei et al., 2020) lead to imple­
mentation in building-integrated photovoltaics, portable power sources,
powering of drones, etc (Kim et al., 2021). However, to achieve desired
phases without other secondary phases is a skilled task. However, the
PCE of single-junction thin-film solar cells is a mere ~ 23 % despite
endless efforts from various research groups for the last three decades
(He, M. et al., 2021). Moreover, third-generation solar cells such as dye-
sensitized solar cells, (Karthikeyan et al., 2017) organic–inorganic
halide perovskite solar cells, (Manjunath et al., 2019) polymer solar
cells, etc., deliver significantly higher efficiency and lower cost(Mani­
arasu et al., 2018) mimicking the natural photosynthesis process have
posed a challenge to replace first-generation Si solar cells (Kim et al.,
2020). Nevertheless, these perovskite solar cells suffer from thermal,
moisture, and UV interference instability (Aftab and Ahmad, 2021;
Manjunath et al., 2021). Consequently, diverse processes like the use of
protective coatings, (Gao et al., 2019) lower-dimensional perovskites,
(Ge et al.) double perovskites, (Li et al.) and molten ionic salts in syn­
thesis, (Du et al.), etc. are employed by various research groups, but
interface alteration and complex fabrication processes restricted the
cost-effective efficiency and long-term stability, hence require cautious
optimism. Therefore, a cheap/stable alternate light absorber layer with
desired photovoltaic properties is essential to overcome the drawbacks
of the halide perovskite absorber layer.

* Corresponding author.
E-mail address: rupesh@iiti.ac.in (R.S. Devan).
1
Authors with equal contributions.

https://doi.org/10.1016/j.solener.2022.08.034
Received 28 June 2022; Received in revised form 9 August 2022; Accepted 16 August 2022
Available online 24 August 2022
0038-092X/© 2022 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
Y.K. Reddy et al. Solar Energy 244 (2022) 75–83

Fig. 1. (a) Comparison of Shockley-Queisser efficiency limits of various light harvesters. (b) Schematics of proposed CBO and metal sulfide based Kusachiite
solar cells.

On scrutinizing panchromatic visible light absorbers, p-type CBO of

AB2O4 (Kusachiite) spinel structure with tetragonal crystal system,
lately studied for its implementation in solar-driven water splitting, (Liu
et al., 2018) photocatalytic dye degradation, (Sabri et al., 2020), and
antimicrobial applications, (Zhu et al., 2016) shall be an excellent choice
as an absorber layer. Furthermore, CBO, a ternary metal oxide, is non-
toxic, cheap, and ambient friendly and can be synthesized using
various techniques ranging from solution processing to vacuum depo­
sition. Moreover, the solar cell utilizing CBO light absorber can achieve a
higher side of Shockley-Queisser limit than that of perovskite, CIGS,
CZTS, and c-Si (Fig. 1(a)). On the other hand, owing to the valence
electron shell structure of the 3d orbitals, MSs have shown promise as an
n-type material, emitter, or buffer layer in thin-film solar cells (He, Z.
et al., 2021). The synthesis of MS thin films exhibiting stable physical
and chemical properties and high carrier mobility is feasible from lower
temperature solution or vacuum processes (even over flexible sub­
strates) utilizing cheaper and readily available sources (Fig. 1(b)) (Moon
et al., 2019). Unlike widely used oxide buffer layers, wide bandgap MSs
do not contain oxygen vacancies and facilitate high optical stability
(Ouyang et al., 2019). Recently, Hosen et al. (Hosen et al., 2021)
simulated the capabilities of CBO as an absorber layer in thin-film solar
cells combined with CdS in Al/FTO/CdS/CBO/Ni device architecture
and estimated 26 % PCE for optimum thickness (i.e., 2000 nm) of the
CBO light absorber. However, to our best knowledge, the device archi­
tecture comprising other sulfides and metal contacts has not been
explored to realize the upper PCE limit of MSs/CBO.
Therefore, this study is focused on evaluating the potential of the
CBO absorber layer and also exploring suitable n-type MS with CBO to
form efficient p-n junction thin-film solar cells shown in Fig. 1(b). The
experimental investigation to find suitable MS for CBO is a myriad task;
thereof, researchers usually employ various software packages to iden­
tify the appropriate materials and analyze the variation in solar cell
performance depending on the changes in their optoelectronic proper­
ties (Alla et al., 2022). In general, finite difference time domain method
(FDTD), SILVACO ATLAS, wxAMPS, AFORS-HET, etc., are employed to
simulate solar cells. However, among these software packages, SCAPS-
1D, developed at Gent University, Belgium, offers a simulation of het­ Fig. 2. Energy band diagram of p-type CBO light absorber and various n-type
metal sulfide buffer layers utilized for p-n junction solar cell.
erojunction and multi-junction solar cell devices (Karthick et al., 2020).
Therefore, the suitability of n-type MSs and CBO in thin-film solar cells is
analyzed based on SCAPS-1D simulations for the device structure con­ as n-type materials in combination with CBO light absorber for
sisting of FTO as transparent conducting oxide, n-type MS buffer layer, kusachiite solar cells are discussed comprehensively. The simplified
CBO kusachiite light absorber, and Au counter electrode, as shown in device structure adopted in this study (FTO/MS/CBO/Au) can be
Fig. 1(b). The theoretical studies on the performance of Cadmium sulfide implemented experimentally analogous to third-generation solar cells
(CdS), Tin sulfide (SnS2), Tungsten sulfide (WS2), and Zinc sulfide (ZnS) (perovskite solar cells). The performance of solar cell parameters for

76
Y.K. Reddy et al. Solar Energy 244 (2022) 75–83

Table 1 Table 2
The physical parameters used to analyze and optimize solar cell properties. The defect parameters used to analyze and optimize solar cell properties.
Parameter ITO CdS ZnS SnS2 WS2 CBO Parameters CdS ZnS SnS2 WS2 CBO

Thickness 350 Variable Defect Type Single Single Single Single Single
(nm) Acceptor Acceptor Acceptor Acceptor Donor
Bandgap Eg 3.5 2.4 2.6 1.85 2.1 1.5 Capture cross 1 × 10-15 1 × 10-15 1 × 10-15 1 × 10-15 1 × 10-15
(eV) section of
Electron 4 4.18 3.74 4.26 3.95 3.72 electrons
affinity χ (cm2)
(eV) Capture cross 1 × 10-15 1 × 10-15 1 × 10-15 1 × 10-15 1 × 10-15
Dielectric 9 10 12 17.7 13.6 34 section of
constant holes (cm2)
ε Reference for Above Ev Above Ev Above Ev Above Ev Above Ev
CB effective 2.2 × 2.2 × 2.2 × 7.32 × 2 × 1018 1.2 × defect energy
density 1018 1018 1018 1018 1019 level Et
of states Energy level with 0.6 0.6 0.6 0.6 0.6
Nc respect to
(cm− 3) Reference (eV)
VB 1.8 × 1.9 × 1.8 × 1 × 1019 2 × 1018 5× Defect Energy Gaussian Gaussian Gaussian Gaussian Gaussian
effective 1018 1019 1019 1019 Distribution
density Characteristic 0.1 0.1 0.1 0.1 0.1
of states Energy (eV)
Nv Total defect 1 × 1014 1 × 1014 1 × 1014 1 × 1014 variable
(cm− 3) density (cm− 3)
Thermal 1× 1 × 107 1× 1 × 107 1 × 107 1×
velocity 107 107 107
of
electrons dy d2 Ψ q
Vth,e
= − = [p(x) − n(x) + ND+ (x) − NA− + pt (x) − nt (x)] (1)
dx dx2 ε
(cms− 1)
Thermal 1× 1 × 107 1× 1 × 107 1 × 107 1× where Ψ is the electrostatic potential, q is the electron charge, ε is the
velocity 107 107 107
dielectric constant of the semiconductor material, p is the hole con­
of holes
Vth,p centration, n is the electron concentration, N-A is the density of the
(cms− 1) ionized acceptors, N+D is the density of the ionized donors, nt is the
Electron 20 100 200 50 100 1.1 × trapped electrons, and pt is the trapped holes, and × is the position
Mobility 10-3 coordinate.
µn (cm2
V-1s− 1)
Electron (Equation (2)) and hole (Equation (3)) continuity equations:
Electron 10 25 40 25 25 1.2 ×
dnp np − np0 dE dnp d2 np
mobility 10-3 = Gn − + np μn + μn E + Dn 2 (2)
µp (cm2 dt τn dx dx dx
V-1s− 1)
Ref. (Rai (Salah (Hosen (Haghighi (Islam (Hosen dpn pn − pn0 dE dpn d2 pn
et al., et al., et al., et al., et al., et al.,
= Gp − + p n μp + μp E + Dp 2 (3)
dt τp dx dx dx
2020) 2019; 2020) 2018; 2021; 2021)
Samiee Tripathi Sobayel
et al., et al., et al.,
where Gn and Gp are the electron and hole generation rates, np and pn are
2014) 2021) 2020) the electron and hole concentrations in the p- and n- region, respec­
tively, npo and pno are the equilibrium electron and hole concentrations
in the p- and n- region, τn and τp denotes electron and hole lifetime, μp
simplified device structure of FTO/MS/CBO/Au is evaluated for varia­ and μn are the hole and electron mobilities, E is the electric field, and Dn
tion in thickness, accepter/donor defect, and doping density of subse­
quent thin-films, counter electrodes, and operating temperature.

2. Simulation procedure

The effect of CBO light absorber and MSs (i.e., CdS, SnS2, WS2, and
ZnS) buffer layer on the performance of kusachiite solar cells is analyzed
using SCAPS-1D. The simulations are carried out under AM 1.5G with an
incident power density of 100 mW/cm2. The energy position of CBO
with respect to the MS buffer layer is shown in Fig. 2. The conduction
band offsets between CBO absorber films and CdS, WS2, SnS2, and ZnS
transport layers are 0.39, 0.33, 0.45, and 0.32 eV, respectively, which
offers smooth charge transportation at CBO/MS interface. (Zhou et al.,
2015) The barrier between the valence band maximum of CBO and WO3,
SnO2, ZnO, and TiO2 buffer layer is 1.41, 0.95, 0.83, and 1.38 eV,
respectively, which is sufficiently high to restrict the flow of positive
carriers towards MSs, thus, minimizes recombination at the CBO/MO
interface.
The solar cell performance parameters are evaluated by solving
fundamental semiconductor equations mentioned below, which dictate
the charge transport in the semiconductor, (Manjunath et al., 2022).
Poisson Equation (Equation (1)): Fig. 3. Simulated absorption coefficient of kusachiite CBO light absorber layer.

77
Y.K. Reddy et al.
Fig. 4. The effect of CBO light absorber thickness on the performance of solar
cells comprising 100 nm thick buffer layers of various sulfide films.
and Dp are the electron and hole diffusion coefficients. The carrier
transport occurring by drift and diffusion for electrons (Equation (4))
and holes (Equation (5)) is expressed as:
dn dEFn
Jn (x) = qnμn E + qDn = nμn (4)
dx dx
dp dEFp
Jp (x) = qpμp E − qDp = p μp (5)
dx dx
where EFn and EFp are the quasi-Fermi levels for electrons and holes. The
physical and defect parameters used in the simulation of PSCs are
tabulated in Table 1 and 2. Further, the value of series and shunt
resistance of 5 Ω/cm2 and 1 MΩ/cm2, respectively, are considered for
the solar cells performance optimization.
3. Results and discussions
The high optical absorption coefficient of the light absorbers in a
thin-film format is one of the prerequisites for fabricating efficient solar
cells. Therefore, the optical absorption coefficient of CBO absorbers is
simulated to understand the optical absorption behavior (Fig. 3). Apart
from the broad absorption range in the visible spectrum, the absorption
coefficient of ~ 105 cm− 1 is measured for the CBO film at 550 nm, which
is relatively equivalent to high-efficiency GaAs and perovskite solar cells
(De Wolf et al., 2014). Another key determinant of solar cell perfor­
mance is the charge-carrier diffusion length (LD). A longer LD generally
means a thicker absorber layer for greater light harvesting (Zhao et al.,
2014). An increase in the thickness of CBO absorber film beyond the
charge diffusion length will lead to charge recombination resulting in
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Solar Energy 244 (2022) 75–83
Fig. 5. The effect of acceptor doping density of 900 nm thick CBO light
absorber film on the performance of solar cells comprising various sulfide buffer
layers of 100 nm thickness.
low short circuit current density (JSC), subsequently restraining the PCE
(Xing et al., 2013). Importantly, the CBO thin films deposited by spin-
coating and PLD showed a carrier diffusion length of ~ 50 nm (Ber­
glund et al., 2016; Wang et al., 2017). Moreover, the thickness of the
absorber layer controls the carrier absorption of short-wavelength
photons and considerably reduces the electrical losses associated with
charge carrier recombination at the interface. As the light absorption
takes place throughout the thickness of the absorber, blue light or other
high energy light is absorbed at the interface, whereas the low energy
light like red light will be absorbed when the thickness of the absorber is
on the higher side (Ghosh et al., 2017). Therefore, the thickness of CBO
absorber films requires precise optimization to achieve maximum PCE.
With a constant thickness of 100 nm for n-type MSs films, variation in
the solar cell parameters is estimated for CBO absorber films of various
thicknesses (in the range of 100 to 1500 nm), as shown in Fig. 4. The PCE
value for the solar cells consisting of n-type MSs under study (i.e., CdS,
WS2, SnS2, and ZnS) increased with the thickness of CBO films due to a
corresponding increase in JSC. The maximum PCE of 22.09, 23.6, 21.56,
and 23.1 % is observed for the CdS, WS2, SnS2, and ZnS buffer layers,
respectively, used with a 1500 nm thick CBO absorber layer. However,
JSC and PCE are marginally saturated beyond the CBO thickness of 900
nm for all the MSs buffer layers. Although a similar trend has been
observed for the fill factor (FF) and open-circuit voltage (VOC) after
varying the CBO film thickness, the MS buffer layer has administered the
actual gain in FF and Voc. The marginal change in FF should be
Y.K. Reddy et al.
Fig. 6. The effect of bulk defect density of 900 nm thick CBO light absorber
film on the performance of solar cells comprising various sulfide buffer layers of
100 nm thickness.
addressed mostly as bulk-induced changes, or losses, rather than con­
ventional parasitic changes (Liu et al., 2019). The marginal increment in
the VOC is observed with an increase in absorber thickness because the
band offset between CBO/MSs is independent of the thickness of the
absorber layer and does not contribute to the increment in the PCE
(Balach et al., 2018; Jassim et al., 2013; Vishwakarma, 2015). The solar
cells consisting of n-type WS2 showed maximum efficiency of 22.84 %,
followed by ZnS (22.30 %), CdS (21.30 %), and SnS2 (20.90 %) at the
CBO film thickness of 900 nm.
Considering the marginal enhancement in the PCE beyond 900 nm
thick CBO film, the optimum thickness of 900 nm is considered for CBO
film to evaluate further the effect of other physical parameters like
doping and defect density on the PV performance. Therefore, the
acceptor doping density in CBO films is tuned in search of further
improvement in the PCE. Fig. 5 shows the acceptor doping density-
dependent variation of different solar cell parameters in the CBO
films. As the acceptor doping density in the CBO film increased from
1017 to 1022 cm− 3, the corresponding PCE has increased for all MSs
buffer layers. The highest efficiency of 27.73 % observed for SnS2 might
be because of its high visible light photoactivity, followed by WS2
(26.99 %), CdS (26.48 %), and ZnS (26.24 %). The Voc and FF have
improved with the increase in acceptor doping density, which can be
ascribed to an increase in built-in potential due to modified band offset
between MSs and CBO films and charge conductivity in CBO films,
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Solar Energy 244 (2022) 75–83
Fig. 7. The effect of thickness of MSs buffer layers on the performance of solar
cells comprising 900 nm thick CBO absorber layer.
respectively (Rai et al., 2021). The improved VOC and FF are the sig­
nificant contributors to a substantial rise in PCEs. However, the slight
decrease followed by saturation in JSC can be due to the higher recom­
bination rate and a reduction in charge carrier mobility with varying
acceptor doping density (Rai et al., 2021).
The solution processing or vacuum deposition techniques inculcate
the bulk defect in the deposited film. Therefore, the bulk defect density
of the CBO absorber film shall influence the overall solar cell perfor­
mance. Fig. 6 shows the effect of bulk defect density variation in the CBO
light absorber film on solar cell performance comprising various sulfide
buffer layers. The increase in the bulk defect density in the CBO layer has
reduced the PCE for all distinct n-type MSs buffer layers. Even though
PCE values reduced (21.32 to 2.95 %, 22.84 to 5.08 %, and 22.33 to
2.22 % for CdS, WS2, and ZnS, respectively) with increased bulk defect
density, a lesser reduction is observed for SnS2 (i.e., 20.9 to 7.56 %).
Likewise, a reduction in JSC and VOC is observed with an increase in
defect density in CBO film, but the FF remained reasonably identical.
The reduction in JSC and VOC can be attributed to defect-assisted
recombination in CBO absorber films and change in band offsets be­
tween MS and CBO films resulting from the modification in conduction
and valence band levels of CBO films with increased bulk defect density,
respectively. (Moon et al., 2020) The reason behind identical values of
FF is not well understood. Furthermore, Shockley-Read-Hall (SRH)
recombination model is considered to study the effect of variation in the
bulk defect density of the absorber layer (Equation (6)), where recom­
bination is considered to occur via defect energy levels (also known as
trap levels) which act as a localized recombination center within the
absorber material. This results in the reduction of JSC and VOC of the
device.
Y.K. Reddy et al.
Fig. 8. The effect of donor density of 100 nm thick MSs buffer layers on the
performance of solar cells comprising CBO absorber layer of 900 nm thickness.
( )
np − n2i
RSRH = ( ) (6)
τ n + p + 2ni cosh(Eki −B TEt )
where n and p is the concentration of electron and holes, ni is the
intrinsic carrier concentration, τ is the lifetime of the charge carrier, Ei is
the intrinsic energy level, Et is the energy level of trap states, kB is the
Boltzmann constant, and T is the operating temperature of the solar cell.
Further, to evaluate the optical and electrical properties of the n-type
MSs, the optimized CBO film of 900 nm thickness is considered for the
solar cell. Fig. 7 shows the effect of MS buffer layer thickness on the
performance of kusachiite solar cells. The thickness of MS buffer layers is
varied independently from 30 to 400 nm to avoid blinding irradiation
striking over the CBO absorber films. The PCE and JSC marginally
increased with increasing thickness of the MS buffer layer for all MSs due
to their reasonable visible light photovoltaic activity (He, Z. et al.,
2021). However, VOC and FF have remained constant as the band offset
between the MS, and CBO films remain stable irrespective of the in­
crease in the MS film thickness. The VOC and FF depend on the band
offset energy level and the internal parasitic resistance, which is inde­
pendent of the buffer layer thickness (Liu et al., 2019). However,
considerable variation in FF for the SnS2 buffer layer can be assigned to
the high intrinsic charge conductivity. Moreover, the PCE of kusachiite
solar cells consisting of the SnS2 buffer layer is relatively higher than
that of CdS, ZnS, and WS2, which has also linearly enhanced with
increased thickness due to its high intrinsic visible photovoltaic activity,
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Solar Energy 244 (2022) 75–83
Fig. 9. The effect of work-function of metal back contact on various parameters
of solar cells consisting of optimized CBO and MSs thin layers.
which further added up with the CBO absorber layer. However, an in­
crease in metal sulfide buffer layer thickness beyond 400 nm will pre­
vent irradiation from striking the CBO light absorber and insignificantly
improve the PCE. Therefore, the optimum thickness of 100 nm, where
significantly better PCE values are observed, is considered for all buffer
layers along with the 900 nm CBO absorber layer to evaluate further the
effect of doner density on the PV performance. However, for the SnS2
buffer layer with 400 nm thickness, we were able to achieve maximum
efficiency of ~ 30 % at a higher acceptor doping density of 1022 cm− 3.
Fig. 8 shows the donor doping density-dependent variation (i.e., 1015
to 1022 cm− 3) in the parameters of CBO/MSs kusachiite solar cells. The
increased donor doping density in the MS films has not significantly
altered the PCE, VOC, FF, and JSC. Thus, unlike CBO light absorber films,
the increase in the doping density of MS films had a negligible influence
on solar cell performance; and hence, doping of MSs buffer layers has
shown not much improvement in increasing the charge conductivity and
boost the efficiency of CBO solar cells. Nevertheless, the PCE and JSC
have substantially enhanced with an increase in donor doping density in
buffer layers.
The metals like Ag, Au, Al, Pt, etc., exhibiting distinct work func­
tions, have been explored as the counter electrode or metal back con­
tacts for the commercial solar cells. Their conductivity, cost, and
physical and chemical reactivity directly impact the cost and perfor­
mance of solar cells. Therefore, the effect of the work function of the
metal back contact on the overall performance of solar cells is explored
and shown in Fig. 9. The work function of electron-rich metal back
contact has revealed a direct influence on the performance of solar cells.
The VOC increased sharply up to a work function of 5.1 eV (i.e., Au
Y.K. Reddy et al. Solar Energy 244 (2022) 75–83

Fig. 10. IPCE curves of the kusachiite solar cells for different CBO absorber thicknesses with an optimized thickness of various (a) CdS, (b) WS2, (c) SnS2, and (d) ZnS
buffer layers.

Fig. 11. J-V curves of kusachiite solar cells comprising spinel CBO absorber and n-type CdS, WS2, SnS2, and ZnS buffer layer.

metal) and saturated after that as the holes are easily extracted to metal
surfaces with a work function greater than 5.1 eV. The increase in JSC
with work function can be associated with the variable charge extraction
due to the difference in the work function of the metal counter elec­
trodes. Moreover, the FF and PCE have significantly increased at work-
function of 5.1 eV and thereafter remained relatively perpetual up to 5.7
eV (i.e., Pt metal). The higher PCE and FF values at the work function of
5 eV (i.e., Au metal) indicate the effective hole transfer at the interface of
the metal back contacts and CBO absorber layer. Moreover, the WS2 has
delivered a higher PCE of 22.84 % among all other MS buffer layers
when combined with the CBO absorber layer and Au metal contact.
Analyzing the spectral response of the CBO and metal sulfide-based
kusachiite solar cells is imperative to interpret the overall quantum ef­
ficiency. Fig. 10 shows the incident photon to current efficiency (i.e.,
IPCE) curves of the kusachiite solar cells made of different thicknesses of
CBO absorber film while retaining optimized thickness of 100 nm for
CdS, WS2, ZnS, and SnS2 buffer layers. For all the MS films, with
increasing thickness of CBO absorber film, the quantum efficiency of
solar cells has increased with the CBO absorber thickness generating
larger photoelectrons, irrespective of the kind of metal sulfide used as
the buffer layer. However, further increase in thickness of CBO (i.e.,
greater than 900 nm) restrict the photons from reaching deep inside and
progressively generate the photoelectrons, as noticed in CBO absorber
thickness-dependent studies (Fig. 4). The distinctive bandgap and band-
alignment of MSs and CBO have reflected in two distinct dips in IPCE,
assigned to the MSs buffer layer and CBO absorber, respectively. The
improved IPCE for the SnS2 buffer layer compared to other MSs reflected
through the border curve indicates its better photovoltaic activities with

Fig. 12. Temperature-dependent J-V curves of the kusachiite solar cells containing spinel CBO absorber and n-type MSs buffer layer.

81
Y.K. Reddy et al.
the CBO buffer layer. Moreover, the perfect band alignment of SnS2 and
CBO has shifted this dip to a high wavelength (~826 nm), indicating
excellent transfer of photogenerated electrons at the interface producing
higher IPCE.
Fig. 11 shows the J-V curves of kusachiite solar cells constituted of
spinel CBO absorber and distinct n-type buffer layer of CdS, WS2, SnS2,
and ZnS in the dark and under illumination. The kusachiite solar cells
consisting of CBO absorber layer jointly with n-type WS2 buffer layer
delivered higher efficiency of 22.84 %, which is followed by ZnS (21.94
%), CdS (21.3 %), and SnS2 (20.9 %). The high efficiency of Kusachiite
solar cells with WS2 may be due to lower conduction band offset at CBO
and WS2 interface and low bandgap of WS2 film as compared to other MS
films, as shown in Fig. 2 and Table 1, respectively. However, it is to be
noted that a PCE of 23.15 % can be achieved from 100 nm thick n-type
WS2 buffer layer if one can increase the donor doping density up to 1022
cm− 3 (Fig. 8). Higher efficiency, around 27 %, is observed when the
acceptor doping density is varied.
During the real-time application of solar cells, elevated operating
temperatures increase stresses associated with thermal expansion and
hence play a prominent role in influencing the performance of the cells.
Therefore, the effect of the operating temperature is investigated for the
temperature ranging from 300 to 380 K, and the corresponding simu­
lated J-V curve is shown in Fig. 12. The rise in temperature scales down
the relative VOC by increasing the saturation current flowing opposite to
the direction of the illumination current. Therefore, the increased
operating temperature from 300 to 380 K results in a higher saturation
current, reducing VOC. Further, the change in carrier concentration
partially comes from the reduction in the bandgap and the smearing of
the Fermi distribution. (Sheikh et al., 2017). Though the PCE declines
with the rise in temperature, reasonable higher efficiency of 21.14 % (at
380 K) is still achieved theoretically for kusachiite solar cells bringing
together the 900 nm thick CBO absorber layer and n-type WS2 buffer
layer of 100 nm thickness.
4. Conclusion
In conclusion, an oxide spinel CBO and metal sulfide-based
kusachiite solar cells are theoretically scrutinized for their best perfor­
mance as a visible light harvesters. Various n-type MS buffer layers (CdS,
WS2, SnS2, and ZnS) are analyzed with a p-type kusachiite CBO light
absorber to evaluate theoretically (using SCAPS-1D) the performance of
CBO based solar cells. All these MSs buffer layers used with CBO have
shown efficiencies greater than 20 %. The highest efficiency of 27.73 %
is observed for ITO/SnS2/CBO/Au device structure. Comparatively, the
solar cell device architecture of ITO/WS2/CBO/Au consisting of the
optimized CBO light absorber of the thickness of 900 nm and acceptor
doping density of 2 × 1018 cm− 3 with n-type WS2 buffer layer of 100 nm
thickness and 2 × 1018 cm− 3 donor doping density showed the highest
PCE of 22.84 %. Therefore, synthesis of CBO light absorber using the
cost-effective chemical method and further spin coating or doctor
blading it along with the widely employed MSs buffer layer to form
kusachiite solar cells has tremendous potential to gain higher PCE
experimentally and compete with perovskite solar cell technology.
Overall, the methodology and approach provided here to scrutinize
environmentally friendly, cost-effective, easy to manufacture, and
packaging visible light absorber and metal sulfide buffer layers can be
extended to other optoelectronic devices.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
82
Solar Energy 244 (2022) 75–83
Data Availability Statement.
The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Acknowledgements
Y. K. R. and V. M. have contributed equally to this work. The authors
would like to thank Mr. Marc Burgelman, the Electronics and Informa­
tion Systems (ELIS), University of Ghent, Belgium, for providing us free
access to the SCAPS 1D simulation tool on request. The authors would
like to thank TARE-DST India for their financial support for this research
under grant No. TAR/2019/000106.
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